JPH0146503B2 - - Google Patents
Info
- Publication number
- JPH0146503B2 JPH0146503B2 JP59172541A JP17254184A JPH0146503B2 JP H0146503 B2 JPH0146503 B2 JP H0146503B2 JP 59172541 A JP59172541 A JP 59172541A JP 17254184 A JP17254184 A JP 17254184A JP H0146503 B2 JPH0146503 B2 JP H0146503B2
- Authority
- JP
- Japan
- Prior art keywords
- naphthalene
- sulfur trioxide
- sulfonation
- sulfonic acid
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 91
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 79
- 238000006277 sulfonation reaction Methods 0.000 claims description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 28
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 28
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 24
- 239000012433 hydrogen halide Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 150000001491 aromatic compounds Chemical class 0.000 claims description 17
- -1 Aromatic sulfonic acids Chemical class 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 54
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 23
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 16
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- 239000011541 reaction mixture Substances 0.000 description 14
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 12
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- XTEGVFVZDVNBPF-UHFFFAOYSA-N naphthalene-1,5-disulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1S(O)(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-N 0.000 description 10
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- SGBQUMZTGSQNAO-UHFFFAOYSA-N 2-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(O)=CC=C21 SGBQUMZTGSQNAO-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229950011260 betanaphthol Drugs 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- 125000006267 biphenyl group Chemical group 0.000 description 6
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical class C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- HEWDOWUUTBCVJP-UHFFFAOYSA-N naphthalene-1,6-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 HEWDOWUUTBCVJP-UHFFFAOYSA-N 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- YOCANESYZHRYBP-UHFFFAOYSA-N 2-hydroxynaphthalene-1,6-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=CC2=C(S(O)(=O)=O)C(O)=CC=C21 YOCANESYZHRYBP-UHFFFAOYSA-N 0.000 description 2
- VVPHSMHEYVOVLH-UHFFFAOYSA-N 6-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=CC2=CC(O)=CC=C21 VVPHSMHEYVOVLH-UHFFFAOYSA-N 0.000 description 2
- HUYJTJXLNBOVFO-UHFFFAOYSA-N 7-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(O)=CC=C21 HUYJTJXLNBOVFO-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- CGEXUOTXYSGBLV-UHFFFAOYSA-N phenyl benzenesulfonate Chemical class C=1C=CC=CC=1S(=O)(=O)OC1=CC=CC=C1 CGEXUOTXYSGBLV-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical group CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- URNUWVIPNDXJGL-UHFFFAOYSA-N 2-chloro-1-(6-methoxy-2,2,4-trimethyl-3,4-dihydroquinolin-1-yl)ethanone Chemical compound ClCC(=O)N1C(C)(C)CC(C)C2=CC(OC)=CC=C21 URNUWVIPNDXJGL-UHFFFAOYSA-N 0.000 description 1
- ZTDJDNLZVGJTBW-UHFFFAOYSA-N 4-methylnaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(C)=CC=C(S(O)(=O)=O)C2=C1 ZTDJDNLZVGJTBW-UHFFFAOYSA-N 0.000 description 1
- SCOSSUFXFMVRJQ-UHFFFAOYSA-N 6-hydroxynaphthalene-1-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC2=CC(O)=CC=C21 SCOSSUFXFMVRJQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FKORGLNGEASTQE-UHFFFAOYSA-N naphthalene-1,3-disulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC(S(O)(=O)=O)=C21 FKORGLNGEASTQE-UHFFFAOYSA-N 0.000 description 1
- HYFMZOAPNQAXHU-UHFFFAOYSA-N naphthalene-1,7-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(S(=O)(=O)O)=CC=C21 HYFMZOAPNQAXHU-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B45/00—Formation or introduction of functional groups containing sulfur
- C07B45/02—Formation or introduction of functional groups containing sulfur of sulfo or sulfonyldioxy groups
Description
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æ°èŠãªè£œé æ¹æ³ã«é¢ãããã®ã§ãããDETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing aromatic sulfonic acids by sulfonating aromatic compounds using sulfur trioxide.
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ãã Processes for the preparation of aromatic sulfonic acids by sulfonation of aromatic compounds using sulfur trioxide are known (e.g. EE Gilbert,
Chemical Revue 62 (1962), pp. 549-589).
A disadvantage of using sulfur trioxide as a sulfonating agent is that considerable amounts of undesirable by-products are often produced during these sulfonation reactions, which are difficult to remove due to the high reactivity of sulfur trioxide. It is.
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æããã Sulfur trioxide and ethers, such as dioxane,
If the reactivity of sulfur trioxide is reduced by the preparation of complexes with tertiary amines, such as pyridine, or carboxylic acid amides, such as dimethylformamide, sulfur trioxide can be used as a relatively quiet compound. Sulfonation is obtained. Although the sulfonation reactions using these sulfur trioxide complexes proceed relatively selectively in nature, i.e. the production of relatively few by-products, they are particularly suitable for sulfonation reactions on an industrial scale. In some cases, the complexing agents obtained in stoichiometric amounts have to be recovered for cost and effluent contamination reasons, or their non-recovery results in significant contamination of the effluent; As a result, sulfonation using sulfur trioxide has the major drawback of at least partially detracting from the benefits it provides.
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ã«äŒŽãé«ãè²»çšã«ããã劚ããããŠããã Instead of reactive sulfur trioxide, chlorosulfonic acid has also already been used as a sulfonating agent. Because of its weak sulfonating action compared to sulfur trioxide, the use of chlorosulfonic acid offers improved selectivity and consequent side effects, especially in the sulfonation of easily sulfonated aromatic compounds. A reduction in biological production is obtained. However, the use of chlorosulfonic acid as a sulfonating agent has the major drawback that stoichiometric amounts of hydrogen chloride are obtained as a by-product, and these must be decomposed, i.e. rendered harmless by neutralization. The reason for this is that they cannot be reused for the production of chlorosulfonic acid, since incorporating reuse would involve huge technical outlays. This means that although chlorosulfonic acid itself is an advantageous sulfonating agent for sensitive aromatic compounds, its use for industrial sulfonation reactions is limited by a) sulfur trioxide. This is hampered by its relatively high price, and b) by the high costs associated with detoxifying the hydrogen chloride produced in equimolar amounts during the sulfonation.
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ãèŠåºããã Surprisingly, we have found that hydrogen halides are excellent agents for reducing the reactivity of sulfur trioxide. Due to the reactivity of sulfur trioxide, it is easily sulfonated by hydrogen halides, so even sensitive aromatic compounds, which require quiet sulfonation, can be collectively sulfonated with sulfur trioxide in remarkable yields. I have found that it can be reduced to the extent that it is possible. The reactivity of sulfur trioxide is
It has been found that by establishing a certain hydrogen halide concentration in the reaction mixture, it is possible to match the sulfonability of the aromatic compounds to be sulfonated.
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ãæ¹æ³ã«é¢ãããã®ã§ããã Therefore, the present invention is characterized in that the sulfonation is carried out in the presence of hydrogen halide.Aromatic sulfonic acids are produced by sulfonating aromatic compounds using sulfur trioxide in an organic solvent. It's about how to do it.
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žã§ããã Hydrogen chloride is preferably used as hydrogen halide. The hydrogen halide can be added neat to the sulfonation mixture, for example as gaseous hydrogen chloride, or in the form of compounds which liberate or generate hydrogen halide under the reaction conditions in the reaction mixture. An example of such a compound that produces hydrogen halide (hydrogen chloride) in the reaction mixture under the reaction conditions is chlorosulfonic acid.
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ååç©ã«å ããããšãã§ããã Hydrogen halide can be added to the compound to be sulfonated before or simultaneously with the addition of sulfur trioxide.
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åã§ããã The deactivation effect of hydrogen halide depends on the amount used, and the greater the amount of hydrogen halide, the greater the deactivation of sulfur trioxide.
As a result, more halogenation occurs in the sulfonation of particularly sensitive aromatic compounds that are easily sulfonated than in the sulfonation of relatively less sensitive aromatic compounds that are less easily sulfonated. Hydrogen is used. For the sulfonation of particularly sensitive aromatic compounds, it is suitable to use more than 1 mol of hydrogen halide per mol of sulfur trioxide. However, for the desired deactivation of sulfur trioxide, there is generally a sub-stoichiometric deficit (based on sulfur trioxide).
stoichometric amounts) of hydrogen halide,
For example 0.01-0.9 mol, preferably 0.1-0.8 mol and especially 0.25- mol per mol of sulfur trioxide.
It is sufficient to use 0.75 mol of hydrogen halide.
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äžããã The process according to the invention is particularly suitable for the selective monosulfonation of easily sulfonated aromatic compounds, such as naphthalene, 1-methylnaphthalene, 2-hydroxynaphthalene and diphenyl. These compounds can be selectively sulfonated with high yields by the process according to the invention to give naphthalene-1-sulfonic acid, 1-methylnaphthalene-4
-Sulfonic acid, 2-hydroxynaphthalene-1-
Gives sulfonic acid and diphenyl-4-sulfonic acid.
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ããªæ¹æ³ã§ãåŠçãããã In the treatment of the sulfonated mixtures obtained by the sulfonation of aromatic compounds with chlorosulfonic acid, the equimolar amount of hydrogen chloride formed during the reaction is either decomposed by expensive methods or made pure for further use. The hydrogen halide-containing sulfonated mixtures obtained by the process according to the invention can be converted into pure hydrogen chloride or pure hydrochloric acid or chlorosulfonic acid without loss of hydrogen halide but with e.g. They are processed in such a way that they are collected together and reused in the next batch.
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ããããŠæ¬¡ã®ãããã§å䜿çšãããã The process according to the invention uses sulfur trioxide to treat sensitive aromatic compounds without liberating or forming during the sulfonation complexing agents or other compounds such as hydrogen chloride, which must be recovered or rendered harmless. It is of great industrial importance because it allows selective sulfonation of species. Apart from the desired aromatic sulfonic acids and negligible amounts of by-products, no other compounds are produced during the preparation according to the invention. The hydrogen halide is recovered and reused in the next batch.
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ããŠãããšèšŒæãããŠããã Inert organic solvents which are suitable for the process according to the invention do not react with the sulfur trioxide under the reaction conditions, or at least do not react to an appreciable extent, and at the same time have a good dissolving power for the hydrogen halide. These are solvents with Examples of such solvents are aliphatic halogenohydrocarbons such as tetrachloroethane, 1,2-dichloroethane and 1,2-
It is dichloropropane. Methylene chloride has proven particularly suitable.
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ã«ãããŠå®æœãããã The process according to the invention is carried out at temperatures of -40 to +20°C, preferably -30 to +10°C and especially -20 to 0°C.
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ã«äœ¿çšãããã Sulfur trioxide can be used in the process according to the invention in liquid or gaseous form or in the form of a solution in an inert organic solvent. gaseous sulfur trioxide, optionally diluted with an inert gas such as nitrogen;
Alternatively, solutions of sulfur trioxide in methylene chloride are preferably used.
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ã³åæ°ŽçŽ æ¿åºŠãå¶å®ã§ããã The sulfonation process according to the invention can be carried out in various ways. The aromatic compound to be sulfonated, e.g. naphthalene, is dissolved or suspended in an inert organic solvent, e.g. methylene chloride, and a hydrogen halide, e.g. hydrogen chloride, is dissolved or suspended in the solution or suspension. The process can be carried out, for example, by passing the suspension until it has absorbed the desired amount of hydrogen halide. Then add sulfur trioxide. Sulfonation can be carried out under normal pressure or under elevated pressure. During the addition of sulfur trioxide, various constant hydrogen halide concentrations can be established in the reaction mixture by appropriate selection of pressure and temperature factors and an inert organic solvent with the desired dissolving power for the hydrogen halide.
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ã€ãŠããã Another embodiment consists in simultaneously adding hydrogen halide and sulfur trioxide to a solution or suspension in an organic solvent of the aromatic compound to be sulfonated.
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åæã«èšéæ·»å ããããšãã§ããã A third method is to obtain the hydrogen halides required for the process according to the invention directly in the reaction mixture, for example by partially sulfonating the aromatic compounds with chlorosulfonic acid in an inert solvent, in which case the hydrogen halides produced are From the preparation, note that the hydrogen chloride reaction remains in the mixture, and then complete the sulfonation by adding the amount of sulfur trioxide required for complete sulfonation. ing. In this embodiment, instead of adding all of the chlorosulfonic acid at the beginning, only a portion of the chlorosulfonic acid is added initially, and as this reacts to form hydrogen chloride, the remaining amount of chlorosulfonic acid is used for sulfonation. It can also be metered in at the same time as the required amount of sulfur trioxide.
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§ïŒã The sulfonic acids obtained by the process according to the invention, such as naphthalene-1-sulfonic acid, 2-hydroxynaphthalene-1-sulfonic acid and diphenyl-4-sulfonic acid, are useful for the production of dyes, plant protection agents and emulsifiers. They are important precursors and intermediates (see, for example, Ullmann's Encyclopédie der Technissien Chemie, 4th edition, Vol. 17, pp. 117-94 and Vol. 18, p. 219).
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(0.5 mol) of naphthalene was dissolved in 250 ml of anhydrous methylene chloride. The solution was cooled to -20°C.
9.2 g (0.25 mol) of hydrogen chloride gas were first passed into the resulting suspension with stirring for about 30 minutes. 40 g (0.5 mol) of gaseous sulfur trioxide was then passed over the surface of the stirred naphthalene/methylene chloride suspension using dry nitrogen for 1 hour at -20°C, also with stirring. . The reaction mixture was then stirred at â20 °C for 2 h, then
Pour into 500g of ice-water mixture.
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ïŒãå«æããŠããã The methylene chloride phase was separated, extracted twice with 250 ml of water each time and concentrated to dryness in vacuo. According to analysis by gas chromatography, the residue (5.9 g) contained 73.2% by weight of naphthalene (=6.7% of the naphthalene used).
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ã§ã«ããã The combined aqueous phases were subjected to a brief initial distillation in vacuo to remove the methylene chloride residue, and the aqueous phases were transferred to a 1 liter measuring flask and made up to 1 liter.
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ïŒã High pressure liquid chromatography (HPLC) of this solution showed the following content of naphthalene-sulfonic acids: 89.0 g of naphthalene-1-sulfonic acid, (=85% of theory based on the naphthalene used: = 91.8% of theory based on naphthalene reacted), 6.2 g naphthalene-2-sulfonic acid, (= 91.8% of theory based on naphthalene used)
6.0%: = 6.5% of theory, based on reacted naphthalene) and 0.4 g of naphthalene-disulfonic acids (= 0.28% of theory, based on naphthalene used: = theory, based on reacted naphthalene). 0.3% of the value).
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žã§ãã€ãã The sulfonation described above was repeated, the only difference being that it was not permeable to hydrogen chloride. The yield of naphthalene sulfonic acids in this case (% of theoretical value based on reacted naphthalene) is 76.0% naphthalene-1-sulfonic acid, 8.4% naphthalene-1-sulfonic acid.
2-sulfonic acid, 0.4% naphthalene-1,3-
disulfonic acid, 10.4% naphthalene-1,5-disulfonic acid, 2.7% naphthalene-1,6-disulfonic acid and 0.6% naphthalene-1,7-disulfonic acid.
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æã«èšéæ·»å ãããExample 2 The process carried out was as described in Example 1, except that hydrogen chloride and sulfur trioxide were metered in simultaneously.
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žé¡ã§ãã€ãã The yield of naphthalene sulfonic acids (% of theory based on reacted naphthalene) was 90.0% naphthalene-1-sulfonic acid, 7.3% naphthalene-1-sulfonic acid,
2-sulfonic acid and 0.3% naphthalene-disulfonic acids.
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žé¡ã§ãã€ãã In this process, the yield of naphthalene sulfonic acids (% of theory based on reacted naphthalene) is:
It was 89.9% naphthalene-1-sulfonic acid, 9.8% naphthalene-2-sulfonic acid and 0.5% naphthalene-disulfonic acids.
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æããªããå ãããExample 4 A solution of 25.6 g (0.2 mol) of naphthalene in 250 ml of dry methylene chloride was cooled to -20 DEG C. in the sulfonation apparatus described in Example 1. Dry hydrogen chloride is passed through the solution at a rate of 8 liters/hour, and a solution of 16 g (0.2 mol) of sulfur trioxide in 150 ml of methylene chloride, which has been simultaneously cooled to -10°C, is heated at -20°C for 2 hours. Add with cooling and stirring.
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ãã The reaction mixture was then stirred at -20°C for 2 hours and then processed as described in Example 1.
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žã§ãã€ãã Yield of naphthalene sulfonic acids (% of theory based on reacted naphthalene) according to HPLC
is 89.0% naphthalene-1-sulfonic acid, 10.0
% naphthalene-2-sulfonic acid, 0.6% naphthalene-1,5-disulfonic acid and 0.2% naphthalene-1,6-disulfonic acid.
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åŠãåŠçãããExample 5 In the sulfonation apparatus described in Example 1, a solution of 25.6 g (0.2 mol) naphthalene in 250 g dry methylene chloride was cooled to -20°C. â20
While stirring at °C, a solution of 18 g (0.15 mol) of chlorosulfonic acid in 50 g of dry methylene chloride is first added over 10 minutes, and 4 g (0.05 mol) of trioxide, which has been cooled to -10 °C. of sulfur
A solution of 50 g of dry methylene chloride was then added over 20 minutes. The reaction mixture was stirred at -20°C for 2 hours and then worked up as described in Example 4.
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žã§ãã€ãã Yield of naphthalene sulfonic acids (% of theory based on reacted naphthalene) according to HPLC
is 91.0% naphthalene-1-sulfonic acid, 8.6
% naphthalene-2-sulfonic acid, 0.1% naphthalene-1,5-disulfonic acid and 0.1% naphthalene-1,6-disulfonic acid.
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žã§ãã€ãã When the chlorosulfonic acid solution and the sulfur trioxide solution were added simultaneously, the yield of naphthalenesulfonic acids (% of theory based on reacted naphthalene) was 89.7% naphthalene-1-sulfonic acid,
They were 9.2% naphthalene-2-sulfonic acid, 0.7% naphthalene-1,5-disulfonic acid and 0.3% naphthalene-1,6-disulfonic acid.
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æ·»å ãããExample 6 The process carried out was as described in Example 5, except that in each case 50 g of methylene chloride were added to 12 g (0.1 mol) of chlorosulfonic acid and 8 dl (0.1 mol) of sulfur trioxide. The medium solution was added dropwise over 30 and 90 minutes, respectively, in place of the chlorosulfonic acid and sulfur trioxide used in Example 5.
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žã§ãã€ãã Yield of naphthalene sulfonic acids (% of theory based on reacted naphthalene) according to HPLC
is 89.0% naphthalene-1-sulfonic acid, 10.0
% naphthalene-2-sulfonic acid, 0.6% naphthalene-1,5-disulfonic acid and 0.2% naphthalene-1,6-disulfonic acid.
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äŸïŒäžã«èšãããŠããåŠãããŠåŠçãããExample 7 154 g (1.00 g) in a 2 liter sulfonator
mol) of diphenyl was dissolved in 1000 ml of anhydrous methylene chloride. 7.3 g (0.20 mol) of hydrogen chloride gas was passed into the solution at -10 DEG C. with stirring. 77 g (0.96 mol) of gaseous sulfur trioxide was then passed over the surface of the solution of diphenyl and hydrogen chloride in methylene chloride for 2 hours, also at -10 DEG C., with stirring. The reaction mixture was then stirred at -10°C for 1 hour. The sulfonation mixture was treated as described in Example 1.
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ã€ãã Yield of diphenyl sulfonic acids (% of theory based on reacted diphenyl) according to HPLC
is 99.4% diphenyl-4-sulfonic acid and
It was 0.5% diphenyl-4,4'-disulfonic acid.
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ãããExample 8 A solution of 30.8 g (0.2 mol) of diphenyl in dry methylene chloride is added to a solution of 16 g (0.2 mol) of sulfur trioxide cooled to -10°C as described in Example 4. The reaction was carried out with a solution in dry methylene chloride while passing about 8 liters/hour of dry hydrogen chloride.
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ã€ãã Yield of diphenyl sulfonic acids (% of theory based on reacted diphenyl) according to HPLC
is 98.3% diphenyl-4-sulfonic acid and
It was 0.7% diphenyl-4,4'-disulfonic acid.
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æ°Žã§ïŒãªããã«ãŸã§ã«ãããExample 9 In the sulfonation apparatus described in Example 1, 28.8 g (0.2 mol) of 2-hydroxynaphthalene were dissolved in dry methylene chloride at 40°C. The solution was cooled to -20°C. A solution of 16 g (0.2 mol) of sulfur trioxide in 50 g of dry methylene chloride is passed uniformly at a rate of 8 liters/hour into the suspension that produced dry hydrogen chloride and is simultaneously cooled to -10°C. Added with cooling and stirring at -20°C over approximately 1 hour. The reaction mixture was then stirred at -20°C for 2 hours, after which the temperature was allowed to rise.
Pour into approximately 100 g of ice-water mixture while keeping the temperature below 20°C. In the two-phase reaction mixture obtained in this way, a PH value of 7 was established by addition of 50% strength sodium hydroxide solution. After separating the methylene chloride phase, solvent residues were removed by initial distillation in vacuo, which was transferred to a weighing flask and made up to 1 liter with water.
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žã§ãã€ãã According to HPLC, the yield of 2-hydroxynaphthalenesulfonic acids (% of theory based on reacted 2-hydroxynaphthalene) was 92.8% 2-hydroxynaphthalenesulfonic acids.
Hydroxynaphthalene-1-sulfonic acid, 0.5%
2-hydroxynaphthalene-5-sulfonic acid,
0.5% 2-hydroxynaphthalene-6-sulfonic acid, 3.0% 2-hydroxynaphthalene-8-
sulfonic acid and 0.6% 2-hydroxynaphthalene-1,6-disulfonic acid.
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žã When the above sulfonation of 2-hydroxynaphthalene is carried out in the absence of hydrogen chloride, 2-
The following yields of hydroxynaphthalene sulfonic acids (% of theory based on reacted 2-hydroxynaphthalene) were obtained: 83.5% 2-hydroxynaphthalene-1-sulfonic acid, 2.1% 2-hydroxynaphthalene. -5-sulfonic acid, 0.4% 2-hydroxynaphthalene-6-sulfonic acid,
6.9% 2-hydroxynaphthalene-8-sulfonic acid, 1.0% 2-hydroxynaphthalene-1,
6-disulfonic acid and 0.4% 2-hydroxynaphthalene-6,8-disulfonic acid.
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ããExample 10 In a 1 liter sulfonation beaker equipped with a bottom outlet and a glass frit added to the top of this outlet, 64.1 g (0.5 mol)
of naphthalene in 250 ml of anhydrous methylene chloride was cooled to -20°C. Dry hydrogen chloride was passed through the resulting suspension at â20° C. until saturation was obtained (ie, until approximately 15 g of HCl had been absorbed). 40 g (0.5 mol) of sulfur trioxide was then passed over the surface of the naphthalene suspension in methylene chloride containing hydrogen chloride for about 1.5 hours at -20 DEG C. with stirring. The reaction mixture was then heated to -20°C for approximately 1.5
Added with stirring over a period of time. The reaction mixture was then stirred for 2 hours at â20° C. and then transferred from the hydrogen chloride-containing mother liquor with dry nitrogen through a frit and a bottom outlet into a 1 liter sulfonation beaker equipped with a second similar apparatus. The precipitate was isolated by force addition and the precipitate on the frit was washed with 50 ml of dry methylene chloride.
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žé¡ã§ãã€ãã The composition of the methylene chloride-wet product filtered off with suction was determined by HPLC. It was 91.6% by weight naphthalene-1-sulfonic acid, 2.3% by weight naphthalene-2-sulfonic acid and 0.6% by weight naphthalene-disulfonic acids.
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ã®çæç©ãæ°ãã也ç¥å¡©åã¡ãã¬ã³ã§æŽæµããã The combined filtrate solution and wash solution in a second sulfonation beaker were cooled to -20°C and 64.1 g (0.5 mole) of finely powdered naphthalene was added. Dry hydrogen chloride was again passed through the suspension until saturation was obtained (approximately 4 g of HCl was required here). Sulfonation was then carried out as in the previous batch by passing sulfur trioxide over the surface of the stirred suspension of naphthalene in methylene chloride containing hydrogen chloride. When the reaction was complete, the mother liquor was again forced into the first sulfonation beaker with dry nitrogen and the product on the frit was washed with fresh dry methylene chloride.
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žé¡ã§ãã€ãã The composition of the methylene chloride-wet product was determined by HPLC. It is 86.4% by weight naphthalene-1
-sulfonic acid, 4.1% by weight naphthalene-2-sulfonic acid and 0.3% by weight naphthalene-disulfonic acids.
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ãã In this semi-continuous process, after a saturation concentration has been established for each sulfonic acid in the mother liquor,
That is, the yield of sulfonic acids (% of theoretical value based on reacted naphthalene) after the fifth batch was 91.7% naphthalene-1-sulfonic acid, 6.2% naphthalene-2-sulfonic acid and It was 0.3% naphthalene-disulfonic acids.
Claims (1)
ããããšãç¹åŸŽãšãããè³éŠæååç©é¡ãææ©æº¶
åªé¡äžã§äžé žåç¡«é»ãçšããŠã¹ã«ãã³åããããš
ã«ããè³éŠæã¹ã«ãã³é žé¡ã補é ããæ¹æ³ã ïŒ ããã²ã³åæ°ŽçŽ ãïŒã¢ã«ã®äžé žåç¡«é»åœãã
0.01ã0.9ã¢ã«ã®éã§äœ¿çšããããšãç¹åŸŽãšãã
ç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒã®æ¹æ³ã ïŒ å¡©åæ°ŽçŽ ãããã²ã³åæ°ŽçŽ ãšããŠäœ¿çšããã
ãšãç¹åŸŽãšããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒãŸãã¯ïŒé ã«
èšèŒã®æ¹æ³ã ïŒ ã¹ã«ãã³åãâ40âãïŒ20âã®æž©åºŠã«ãããŠ
å®æœããããšãç¹åŸŽãšããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒã
ïŒé ã®äœããã«èšèŒã®æ¹æ³ã ïŒ å¡©åã¡ãã¬ã³ãææ©æº¶åªãšããŠäœ¿çšããããš
ãç¹åŸŽãšããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒãïŒé ã®äœãã
ã«èšèŒã®æ¹æ³ã[Scope of Claims] 1. Aromatic sulfonic acids by sulfonating aromatic compounds with sulfur trioxide in an organic solvent, characterized in that the sulfonation is carried out in the presence of hydrogen halide. How to manufacture. 2 Hydrogen halide per mole of sulfur trioxide
A method according to claim 1, characterized in that it is used in an amount of 0.01 to 0.9 mol. 3. The method according to claim 1 or 2, characterized in that hydrogen chloride is used as the hydrogen halide. 4. Claims 1 to 4, characterized in that the sulfonation is carried out at a temperature of -40°C to +20°C.
The method described in any of Section 3. 5. The method according to any one of claims 1 to 4, characterized in that methylene chloride is used as the organic solvent.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19833330334 DE3330334A1 (en) | 1983-08-23 | 1983-08-23 | METHOD FOR SULFONING AROMATIC COMPOUNDS WITH SULFUR TRIOXIDE |
DE3330334.7 | 1983-08-23 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6061560A JPS6061560A (en) | 1985-04-09 |
JPH0146503B2 true JPH0146503B2 (en) | 1989-10-09 |
Family
ID=6207193
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59172541A Granted JPS6061560A (en) | 1983-08-23 | 1984-08-21 | Sulfonation of aromatic compounds with sulfur trioxide |
Country Status (4)
Country | Link |
---|---|
US (1) | US4859372A (en) |
EP (1) | EP0141928B1 (en) |
JP (1) | JPS6061560A (en) |
DE (2) | DE3330334A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4007603A1 (en) * | 1990-03-09 | 1991-09-12 | Henkel Kgaa | METHOD FOR PRODUCING NAPHTHALINE SULPHONIC ACIDS |
US20080139840A1 (en) * | 2006-11-03 | 2008-06-12 | Matthew Thomas Anderson | Process for preparing alkyl aryl sulphonic acids and alkyl aryl sulphonates |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3155716A (en) * | 1961-09-29 | 1964-11-03 | American Cyanamid Co | Preparation of pure alpha-naphthalene sulfonic acid and alpha-naphthol |
CH439265A (en) * | 1964-07-16 | 1967-07-15 | Sandoz Ag | Process for the preparation of α-naphthalenesulfonic acid |
GB1434020A (en) * | 1972-10-30 | 1976-04-28 | Koebner A | Sulphonation of aromatic compounds in the presence of solvents |
DE2728070A1 (en) * | 1977-06-22 | 1979-01-11 | Bayer Ag | CONTINUOUS PRODUCTION OF NAPHTHALIN-1-SULPHONIC ACID AND 1,5-DISULPHONIC ACID |
-
1983
- 1983-08-23 DE DE19833330334 patent/DE3330334A1/en not_active Withdrawn
-
1984
- 1984-08-13 DE DE8484109627T patent/DE3462034D1/en not_active Expired
- 1984-08-13 EP EP84109627A patent/EP0141928B1/en not_active Expired
- 1984-08-21 JP JP59172541A patent/JPS6061560A/en active Granted
-
1989
- 1989-01-06 US US07/296,396 patent/US4859372A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP0141928B1 (en) | 1987-01-14 |
JPS6061560A (en) | 1985-04-09 |
DE3330334A1 (en) | 1985-03-14 |
EP0141928A1 (en) | 1985-05-22 |
US4859372A (en) | 1989-08-22 |
DE3462034D1 (en) | 1987-02-19 |
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